Plied aqueous cellulose film



Sept. 4, 1934. F. w. HOCHSTETTER PLIED AQUEOUS CELLULOSE FILM Fled'Sept. 26, 1927 L Q w m M me M, Nn/ mmm SAU NM NEM M2M NMV Nn A @V .|I u .l t .ll rl. rl. H QN. WHHHNHWMHHL n @U Q EN @EN Q Patented Sept. 4, 1934 UNITED STATES PATENT OFFICE Claims.

This invention relates to plied films derived from aqueous cellulose, and more particularly, to lms used in the photographic and other arts.

Many attempts have been made to provide plied films, sheets, webs, etc. of aqueous cellulose derivatives but none of such attempts have been successful, to my knowledge, in producing satisfactory plied medium derived from aqueous cellulose for use in the photographic and other arts. Due to the aqueous cellulose derivatives being subjected to absorption of moisture and l when photographic films are subjected to the 5 various photographic solutions for washing, de-

veloping and fixing, the plied medium comes apart. Such plied'mediums as have heretofore been furnished have also provedto be non-commercial due to the contraction and expansion of the product.

An object of .this invention is to provide an aqueous cellulose plied film, or the like, having water resisting and moisture proof qualities.

Another object of this invention is to provide a treated medium that will not contract or expand when subjected to reasonable heat or moisture.

Another object of this invention is to provide a treated medium that will not be attacked by water, alkali or acid solutions such as used in the photographic and allied arts. Such medium shall also be fiexible, non-contractable and non-'inflammable.

Another object of this invention is to provide a medium comprising a plurality of mediumsto form a single medium having a predetermined thickness that shall retain its flexibility and transparency.

A further object of this invention is to provide a exible, transparent, plied film base derived from aqueous cellulose compound having the above characteristics in a single inexpensive operation thus producing a new article of manufacture that shall be cheaper and more expediently manufactured than the Well known film bases made by other processes.

A still further object of this invention is to provide a plied medium adaptable for use as a photographic film base derived from an aqueous cellulose compound and/or compounds, the surfaces of which vary in character and purpose one from the other, viz., one side will absolutely resist the action of all photographic solutions used in the art and the other side Will carry a mordant or substratum that will readily combine and absorb photographic emulsions and or photographic chemical sensitizing compounds.

As -an example of the apparatus I employ in carrying out this invention, reference is made to the accompanying drawing which is' a side elevational view more or less diagrammatic having the side cover removed.

In the drawing of Fig. 1 I have illustrated the process and apparatus for treating and plying together three aqueous cellulose films for producing a thicker film. In Figure 2, I have shown r, an enlarged and somewhat exaggerated perspec- GJ tive section of a completed film in which numeral 50 represents a water resistant and photographic emulsion absorbent outside ply, numeral 51 an intermediate ply, and numeral 52 an outside ply which is absolutely resistant to photographic emulsions and sensitizing compounds. The numeral 53 shows the theoretical protective coating of reaction products and residues formed by the use of light-treated formaldehyde, and, r on the upper outer side 52 by a combination with l 5 cupro-ammonia. In the actual completed film the layers 50, 51, 52, and coating 53 cannot be distinguished; the article looks like a unitary one-piece whole (see Fig. 3). vHowever, it will be understood that any number of lms, sheets 30 or webs may be plied together in accordance with the principle taught by this invention. I, II and III are supply rolls containing the films, strip or sheets l, 2 and 3 respectively. Strip 1 is conveyed over a guide roll 4 through a solution of 85 Water and glycerine (glycerol) A, then through rubber squeeze rolls 5 to remove the excess solution A and aid in uniformly distributing the solution A thereon. Then the medium 1 is further subjected to a substratum B that will serve on one side for combining with photographic emulsions and the other side to aid uniform combination with medium 2, then through squeeze rolls 10 and press rolls l0.

Medium 2 is conveyed from its supply roll over 95 guide roll 6A through a solution of glycerine (glycerol) and Water A', then through rubber squeeze rolls 7 and through feed rolls 8 which serve to draw the medium from the feed roll. The medium 2 is then conveyed through a solution B', through rubber squeeze rolls 9 and further subjected to the action of formaldehyde in a liquid state and then through rubber squeeze rolls 11.

'I'he medium 3 is conveyed from itsn supply roll over guide roll 12, through a solution A", then out of the solution through rubber squeeze rolls 13, over guide roll 14, through solution B" and then through rubber squeeze rolls 15. The components of the various solutions A, A', A", B and B" will hereinafter be described.

After the mediums 1, 2 and 3 have been treated as above described, they are superimposed one upon the other and pass through press rolls 16. Then the plied medium is conveyed longitudinally through compartment D and passed through the various press rolls 17, 18, 19, 20, etc. As the plied medium passes through the press rolls 16 and 17 it is still in a. plastic state and during this time it is subjected to the action of formaldehyde gas or any other suitable gas, vapor or solution I capable of imparting non-absorbent and, moisture resisting characteristics to the medium. A chamber 22 is provided at the -bottom of the compartment D for supplying the gas or its equivalent.

The compartment D is provided with a step temperature control represented in its entirety by 25. The step temperature control comprises a main air duct 26 having auxiliary air ducts 27 connecting the compartment D at a plurality of points substantially as shown by the drawing. The air supply from the main air duct 26 is conditioned in the mannerl Well known in industrial plants. The air is freed from all foreign matter and is delivered to the main air duct 26 by a suitable apparatus (not shown).

Each of the auxiliary air ducts 27 is provided with a temperature regulating device 28 for delivering the air to the compartment D at any predetermined temperature. The compartment is also provided with auxiliary exhaust pipes 29 which are connected to a main exhaust pipe 31 for relieving the compartment D of the used air.

Each of the auxiliary'exhaust air ducts 29 is provided with an exhaust fan 32 or the main air duct 31 may be provided with an exhaust fan (not shown) for drawing the regulated air through the different portions of the compartment D. In this manner it can be seen that diierent portions of the compartments D may be maintained at different temperatures hereinabove referred to as step temperatures. The variation of the temperatures through which the medium passes hastens the evaporation and dry- `ing of the medium and thereby simplies and increases the production of the finished product.

After the mediums 1, 2 and 3 have been treated with the various solutions mentioned above and superimposed one upon the other through the press rolls 16, the medium is then conveyed through any number of predetermined temperatures in the compartment D and passes through a plurality of press rolls such as shown at 17 and 18 during which time it is subjected to the action of formaldehyde gas or its equivalent in order to render the medium and the various coatings of solutions thereon water resisting. As soon as the medium is suicently dry the lower surface of the medium is then subjected to the well known cupro-ammonia solution or an equivalent E for rendering the lower surface absolutely water as well as acid and base resisting. Since cupro-ammonia readily dissolves cellulose, it has been employed here to slightly dissolve the lower surface of the glycerine treated plied fllm and to form therewith upon the evaporation of the, ammonia of the solution, a very impervious, impermeable and impenetrable surface. A reason for the priority of the formaldehyde treatment of the film, is Ato limit the penetration of this cupro-ammonia solution. By the employment of different amounts of formaldehyde, the penetration of the cupro-ammonia solution may be thereby controlled. In other words, it may be allowed to penetrate enough to aid the adhesive mordant in binding the sheets or webs of the lm. In order that the inorganic formaldehyde will form an absolutely non-hydroscopic surface with the organic material of the lm, they are subjected to a strong light F. If the upper or outer web is translucent or transparent, then the light may act upon the inner web and render it moisture proof. And further, if the intermediate web or webs are translucent, then the light need only be directed upon one side of the plied film in order to completely "fix all of its webs or sheets. But, if an opaque film is employed, then lights may be directed to shine on both surfaces of the plied film, and if it is desired to render the intermediate webs moisture proof, they can be subjected to a strong light before the film is plied. By separate treatment of each web, sheet, or layer with formaldehyde and then by subsequent fixing, these layers will have a like and extremely low coeiiicientv of contraction 'and expansion.

g The medium is then passed through press rolls 20, out into a normal atmospheric temperature,

through a plurality of press rolls 33 and onto a' take-up roll 34. The plied medium received by the take up roll 34 has one of its surfaces absolutely moisture proof, while its other surface will resist water, alkali and acid solutions used in the photographic art but is not entirely moisture proof and will be capable of readily combining and absorbing photographic emulsions and or photographic chemical sensitizing compounds.

'(Ihe term aqueous cellulose as used here means any type of cellulose such as paper, silk, or the like, having hydrophil, bibulous, or hydroscopic properties, that is, capable of readily taking up moisture, or having very good absorption properties. If it is desired to provide a transparent web or sheet, the paper or the like may be treated with a hydroxide-the cellulose is thus liquefied and its brousvmaterial is removed.

Then, the liquid may be treated with carbon di-- oxide-thus, resulting in a transparent solution which will readily solidify. But, it must be under- .stood that any suitable method such as carried out in the industry may be employed for this purpose.

1f a finished product is desired for use other than photographic lms such as window panes, wind shields for automobiles and the like Where a transparent medium is desired having both of its surfaces absolutely moisture proof, then it is only necessary to ply together as many mediums as may be required to give the desired thickness to the finished kproduct in the manner described above, then to subject both surfaces of the plied medium to the action cupro-ammonia or its equivalent and treat in the same manner as above described. The finished product will be a noninflammable, non-contractable, transparent medium that will be absolutely moisture proof and water resisting. A product having any desired .ilexibilitymay be obtained by applying more or finished product comprising four mediums plied 15C Glycerine Potassium chrome alum medium would become absolutely moisture proof resistant and thereby comprising the lower surface of the plied medium.

The solutions A, A' and A" consist of water and glycerine and as an example may bevprepared as follows:

Water 3000 cc. 500 cc.

Water 5000 cc.

Water-soaked and melted hard gelatine 400 grams 10% solution of citric acid 200 cc.

Pure alcohol 100 cc.

The hard gelatine is best applied to the solution at a temperature of 140 F. The second solution may consist of:

Coldwater 3000 cc.

30 grams mordant adhesive compound which is best applied to the medium at a temperature of 110 F. Solution B which is a light sensitive adhesive compound and adapted to be applied to every other strip which would be strip No. 2 as illustrated by the drawing this compound may consist of the following components:

Casein--200 drains soaked in water of its equal weight, then add sufficient ammonia to dissolve the casein and water, neutralize the ammonia by adding 400 cc. of 5% citric acid, under constant stirring add 200 cc. of glycerine or an equivalent for more flexibility, followed by 1000 cc. 2% potassium bichromate solution containing liquid ammonia.

According to the number of strips of medium to be plied together, the medium which is adapted to be the adhesive carrier, and or light sensitive adhesive carrier, such as that described for medium 2 above, is subjected to the action of formaldehyde in a liquid state as represented at C.

It will also be understood that the individual .mediums to be plied may be subjected to formaldehyde gas before superimposing them 'together. However this may be done equally satisfactorily after they have been superimposed one upon the other, so long as the formaldehyde gas is applied to the plied medium while the medium is in a plastic state during which time the formaldehyde, gas will penetrate the medium and act upon it as well as the compounds thereon for rendering them water resisting.

An important advantage of this invention is that the medium and the compounds applied thereto for plying the said mediums together are rendered moisture resisting before applying the cupro-ammonia solution. Since the plied medium as well as the adhesive compounds therebetween are moisture resisting, the cupro-ammonia does not attack the inner faces of the plied mediums but acts only upon the surface to which it is applied and the corresponding edges thereof.

Plied mediums treated in this marmer will not contract or expand when subjected to reasonable heat or moisture or both and one side of the medium will be absolutely moisture proof, and water resisting even if soaked in hot or cold water for an indefinite period and the other side will be free from deterioration by water, alkali and acid solutions such as used in the photographic and allied arts, but will readily form a union with photo emulsions and or photographic sensitizing compounds.

A finished product may be attained having any desired flexibility by adding. different amounts of glycerine or other ingredient capable of imparting flexibility to the medium and sincethe plied mediums and the compounds therebetween are rendered moisture resistant, the flexibility of. such mediums will be maintained as the glycerine content therein is protected from any solution which may cause the glycerine to become dehydrated.

Another advantage of thisinvention is the omission of highly inflammable ingredients and costly solvents such as are required in producing other lm bases. This rendersthe process of producing the present film base much cheaper than the well known film bases made by other processes.

LI do not desire to confine this invention to the compounds that are mentioned above because other suitable substances may be used if they nave equivalent qualities and the components of the compounds may be varied in order to give the finished product or certain portions thereof more or less water resisting characteristics. The temperatures stated above are preferred temperatures but it should be understood that fairly satisfactory results may be attained even though the temperatures mentioned are varied.

Each of the various compound containers may be provided with any well known heating apparatus in order to maintain the compound or soluacetate and nitric (Celluloid) species. Of the L latter two species, Celluloid has the best moisture resistant properties but is very brittle and highly inflammable and is not absolutely resistant to photographic solutions. On the other hand, the cupro-ammonia substratum of applicants film is absolutely resistant to photographic solutions.

The purposegofthis application can only serve to disclose the fundamental principle of the invention and it will be understood that the mediums to be plied may be subjected to the combination of the formaldehyde gas or its equivalent and the action of strong light at any number of positions in the appar-atus and obtain satisfactory results therefrom. Other changes, modifications,

substitutions, additions and omissons may be made without departing from the spirit and scope of the appended claims.

I claim:-

1. A product of manufacture of the kind described having a base derivedfrom a translucent and hydrophil aqueous cellulose, said base having integrally combined therewith a solution of glycerol containing 3000 cc. of water and 500 cc. of glycerin, a light-sensitive adhesive compound, and the products of reaction as Well as the unreacted residues of said solution and said coin-4 pound, said compound containing the products of reaction as well as the unreacted residues of 200 drams of water soaked and ammonia dissolved casein, 400 cc. of citric acid (5%), 200 cc. of glycerin, and 1000 cc. of potassium bichromate solution (2%) containing ammonia; the whole constituting a combination for imparting predetermined physical and chmical characteristics to the article.

2. A product of manufacture of the kind described having a base derived from a translucent and hydrophil aqueous cellulose, said base having integrally combined therewith a solution of glycerol, a light-sensitive adhesive compound, formaldehyde, andthe products of reaction and the unreacted residues of said ingredients, and also having integrally combined therewith a solution of formaldehyde and the reaction products as Well as the'unreacted residues of said formaldehyde with respect to therreaction products and residues of said above-mentioned ingredients, and also having integrally combined therewith the reaction products and residues of a light treatment of said last-mentioned formaldehyde; the whole constituting a combination for imparting predetermined physical and chemical characteristics to the article. I

3. A product of manufacture of the kind described having a base derived from a translucent and hydrophil aqueous cellulose, said base having integrally combined therewith a solution of glycerol, a light-sensitive adhesive compound, formaldehyde, and the products of reaction as well as unreacted residues of said ingredients, the article also having integrally combined with one face thereof a cupro-ammonia solution as well as the products of reaction and the unreacted residues of said cupro-ammonia solution with respect to the products of reaction and unreacted residues of said above-mentioned ingredients; the whole constituting a combination for imparting predetermined physical and chemical characteristics to the article.

4. A product of manufacture of the kind described having a base derived from a translucent and hydrophil aqueous cellulose, said base havingfintegrally combined therewith a solution of glycerol, a light-sensitive adhesive compound, formaldehyde, and the products of reaction as Well as the unreacted residues of vsaid solution, said formaldehyde, and said compound; the whole constituting a combination for imparting predetermined physical and chemical character- ,istics to the article.

5. A product of manufacture of the kind de` scribed having a base derived from a translucent and hydrophil aqueous cellulose base, said base having integrally combined therewith a lightsensitive adhesive compound containing the products of reaction of ammonia-dissolved-casein, neutralizing citric acid, glycerin, and a potassium bichromate solution containing ammonia, insofar as their afiinitiesV and concentrations make the same possible, there being certain unreacted contents; the whole constituting a combination for imparting predetermined physical and chemical characteristics to the article.

6. A product of manufacture -of the kind described having a base derived from a translucent and hydrophil aqueous cellulose base, said base having. integrally combined therewith a solution of glycerol containing 3000 cc. water and 500 cc. glycerin, an adhesive mordant compound, and the products of reaction as well as the unreacted residues of said solution and said compound, said compound containing the products of reaction as well as unreacted residues of an admixture of a solution containing 5000 cc. water, 400 grams of water soaked gelatin, 200 cc. citric acid (10%) 100 c c. pure alcohol, in addition to a solution contaning 3000 cc. of water, and 30 grams of potassium chrome alum; the whole constituting a combination for imparting predetermined physical and chemical characteristics to the article. 7. A product of manufacture of the kind described having a base derived from a translucent and hydrophil aqueous cellulose, said base having integrally combined therewith a solution of glycerol, an adhesive mordant compound, and the products of reaction and the unreacted residues of said solution and said compound, and also having integrally combined therewith the products of reaction and the unreacted residues of formaldehyde and the reaction products and residues of said above-mentioned ingredients; the whole constituting a combination for imparting predetermined physical and chemical characteristics to the article.

8. A product of manufacture of the kind described having a base derived from a hydrophil aqueous cellulose', said base having integrally combined therewith a solution of glycerol, an adhesive mordant compound, and the reactive products and unreacted residues of said solution and said compound, said compound containing the products of reaction as well as unreacted residues of an admixture of a solution of gelatin, citric acid, and alcohol, in addition to a solution of water and potassium chrome alum; the whole constituting a combination for imparting predetermined physical and chemical characteristics to the article.

9. .A plied product of manufacture of the kind described having `an inner and outer ply rigidly secured together, each ply having a base derived from a translucent and hydrophil aqueous cellulose, the base of said outer ply having integrally combined therewith a solution of glycerol, a mordant adhesive compound, and the products of reaction as well as unreacted residues of said solution and said compound, the base of said inner ply having integrally combined therewith a solution of glycerol, a light-sensitive adhesive compound, and the products of reaction as well as unreactedresidues of said solution and said compound; the whole constituting a combination for imparting predetermined physical and chemical characteristics to the article.

10. A manufactured film derived from an absorbent and transparent basic aqueous cellulose, the film having a side absorbent to photographic 'emulsion and photographic sensitizing compounds, said film having another side absolutely resistant to water, photographic emulsions, and photographic sensitizing compounds.

FREDERICK W. Hocns'rmrs'a. 

